Composition and method for catalysis using bentonites

ABSTRACT

Maghnia or Mostaganem bentonites, are activated by contacting the Maghnia or Mostaganem bentonite with an acid solution of selected concentration and then drying the Maghnia or Mostaganem bentonite to form an activated bentonite catalyst. This activated bentonite catalyst may be used to polymerize a vinyl, acrylic, cyclic ether, aldehyde, lactone or olefin monomer. In a further embodiment, a perflourinated amine or diamine is synthesized by contacting a Maghnia or Mostaganem bentonite with an acid solution of selected concentration, drying the Maghnia or Mostaganem bentonite, and absorbing a secondary amine with the Maghnia or Mostaganem bentonite to form a perflouroamide iodide salt. The perflouramide idodide salt can then be extracted with a polar solvent and neutralized by the use of a basic solution.

TECHNICAL FIELD OF THE INVENTION

[0001] The present invention relates in general to the polymerization ofcertain monomers and more specifically to the use of Maghnia andMostaganem bentonites as catalysts for polymerization.

BACKGROUND OF THE INVENTION

[0002] The present field of polymerization of monomers is varied intypes of monomers, catalysts, and processes. Often, catalysts used tomake polymers are expensive, may be poisoned by products of the reactionor impurities present in the monomer feed, and contain heavy metals suchas chromium, mercury and cadmium that present environmental disposalproblems for users. Frequently, these catalysts require the use of veryhigh or very low temperatures and high pressures during thepolymerization reaction. Separation of the catalyst from the polymer isnot always possible, making the polymer less desirable for the customer.

[0003] Examples of these problems are found in the polymerization oftetrahydrofuran (THF) and dioxolane (DXL). The cationic polymerizationof THF is now mostly catalyzed with a BF₃/FSO₃H/HClO₄ mixture, or oleum.This reaction requires a promoter, typically an olefin oxide, acetylchloride, acetic anhydride or cetene. Because of the inefficiency of thecatalyst, large amounts of the catalyst and promoter are required, up toone mole of catalyst for one mole of polytetrahydrofuran (PTHF),resulting in a very expensive process. Similarly, DXL is most oftenpolymerized using a BF₃/FSO₃H mixture in the presence of dichloromethanein a nitrogen atmosphere. However, the reaction is not continuous, theyield is poor, and purification of the product from the residual BF₃ isdifficult. As a result of these problems, polydioxolane is notmanufactured on an industrial scale.

[0004] The chemical industry is always looking for new substitutes tothese classical catalysts. For instance, PTHF can now be polymerized ina cost-effective and environmentally appropriate manner using antimonypentachloride as a catalyst and a mixture of carboxylic anhydrides inthe presence of alcohol as a promoter. But while this new manner ofcatalysis has alleviated some of the processing problems, it hasresulted in a polymer that, because of its black color, does not meetindustry needs.

[0005] In addition, toxic catalysts often present problems in themanufacture of polymers used in medical and veterinary procedures. Thoseinstalling these polymers often desire that the polymer be metabolizedby the body after the polymer has performed its function. These types ofpolymers are called “bioresorbable.” Many bioresorbable polymers aresynthesized from lactides. These bioresorbable polymers are frequentlyused for suture strings, suture wire, staples, meshes, and hemostaticclamps. The polylactide are synthesized with the use of catalysts, mostoften a trioxide of antimony and stannous octanoate. These catalysts aretoxic in even trace amounts, necessitating a careful and costlyseparation of the catalyst from the polymer.

SUMMARY OF THE INVENTION

[0006] Accordingly, there is a need for an effective,low-operating-cost, environmentally-appropriate method of polymerizingcertain monomers. We have found that activated Algerian bentonites,particularly those from Maghnia or Mostaganem, at temperatures between0° and 80° C. are capable of catalyzing the polymerization of thesemonomers. The bentonite catalyst is activated by contacting a Maghnia orMostaganem bentonite with an acid solution of selected concentration andthen drying the Maghnia or Mostaganem bentonite.

[0007] In another embodiment of the invention, a vinyl, acrylic, cyclicether, aldehyde, lactone or olefin monomer is polymerized by contactinga Maghnia or Mostaganem bentonite with an acid solution of selectedconcentration, drying the Maghnia or Mostaganem bentonite and thencontacting the vinyl, acrylic, cyclic ether, aldehyde, lactone, orolefin monomer with the Maghnia or Mostaganem bentonite.

[0008] In another embodiment of the invention, a polymer is manufacturedby contacting a Maghnia or Mostaganem bentonite with an acid solution ofselected concentration, then drying the Maghnia or Mostaganem bentoniteand contacting a vinyl, cyclic ether, aldehyde, lactone, acrylic orolefin monomer with the Maghnia or Mostaganem bentonite.

[0009] In a further embodiment of the invention, a perflourinated amineor diamine is synthesized by contacting a Maghnia or Mostaganembentonite with an acid solution of selected concentration, drying theMaghnia or Mostaganem bentonite, and adsorbing a secondary amine withthe Maghnia or Mostaganem bentonite to form a perflouroamide iodidesalt. The perflouramide idodide salt can then be extracted with a polarsolvent and neutralized by the use of a basic solution.

[0010] One advantage of the present invention is that the Maghnia orMostaganem bentonite can be easily activated with a variety of mineralor organic acids, at room temperature or under heat with a simpleprocedure. As another advantage, these catalysts can then initiatepolymerization and copolymerization reactions at relatively lowtemperatures. As a further advantage, the catalysts can be regeneratedeasily, requiring only heating to a temperature above 100° C. As anadditional advantage, the catalysts can be easily separated from thepolymer product for reuse, reducing operating costs as well as disposalcosts.

DETAILED DESCRIPTION OF THE INVENTION

[0011] Bentonites are hydrated aluminosilicates which crystallize inlayers. These bentonites occur naturally and are mined by the NationalCompany of Non-Ferreous Products (Enterprise Nationale des produits nonferreux, ENOF). After crushing, bentonites can be sold under the name of“load bentonite.” Once crushed, activated in hot sulfuric acid (32%-38%in weight), dried, ground, sifted and conditioned, bentonites arecommercialized under the name of “bleaching clay.” Bentonites are oftenused to filter cooking, mineral, and organic oils. When added to calciumcarbonates, but not acid-treated, bentonites are used for oil drillingunder the name of “drilling bentonite.” Bentonites are often utilized asbleaching clays for oils, drilling mud for oil drilling, as stabilizerfor paints and rubbers, and as insulators for foundries. However, use ofbentonites as catalysts is very new, and research and patenting has beenlimited to bentonites found in the United States, with focus on thosefound in Wyoming and Texas. The Algerian bentonites do not have the samephysical and chemical structure as the American bentonites and prior tothis invention, were never tested for their catalytic properties. FIG. 1is a comparison of the composition of American, French and MaghniaAlgerian bentonites.

FIG. 1

[0012] Comparison of the Composition (in %) of American, French, andMaghnia Algerian Bentonites

[0013] (Prior to Treatment) Wyoming Vienne Maghnia Maghnia (USA)(France) (Algeria) (Algeria) SiO2 57.4 50.04 69.39 71.7 Al2O3 20.2720.16 14.67 14.03 Fe2O3 2.92 0.68 1.16 0.71 FeO 0.19 9 CaO 0.23 1.46 0.30.28 MgO 3.13 .23 1.07 0.8 K2O 0.28 1.27 0.79 0.77 Na2O 1.32 trace 0.50.21 TiO2 0.12 0.16 0.15 SO3 0.91 0.34 As 0.05 0.01 Organics/Water 11 11H2O 6.85 26

[0014] Bentonite from Maghnia has 11.9% more SiO₂ than that from Wyomingand 19.35% more than from Montmorillon (Vienne, France). When treatedwith sulfuric acid, this difference is even greater: 14.21% and 21.66%as compared to Wyoming and Vienne bentonites, respectively.

[0015] Bentonite from Maghnia contains 5.60% and 5.49% less Al₂O₃ thanthe Wyoming and Vienne bentonites, respectively. Once treated, thisdifference is 6.24% and 6.13% with respect to the Wyoming and Viennebentonites, respectively. The X-ray diffraction spectra from the 3bentonites are comparable except the peak intensities and the width ofthe interlayer spacing which varies with the chemical composition.However, bands at 3.76, 3.05, 2.97, 2.12, 1.83 Å observed in thespectrum of the Wyoming bentonite are not present in the spectrum of thebentonite from Maghnia. The same main IR bands are observed in thebentonites from Texas, Wyoming, and Maghnia with some variations.However, the bands at 885 cm⁻¹ and 780 cm⁻¹ are absent in the IRspectrum of the Maghnia bentonite. There are also differences in the NMRspectra: Si NMR: The relative intensity of the peak at 93.5 ppm ishigher for the Maghnia bentonite as compared to that of Wyoming andVienne. A1 NMR: The peaks at 68,60, and 2.9 ppm are higher for theMaghnia bentonite. Once treated, the spectrum of the bentonite fromMaghnia shows a higher peak at 2.88 ppm, which is a characteristic ofthe Al³⁺ mobile cations in the interlayer space. When the Maghniabentonite is exchanged with Ca, there is a slight shift of theoctahedral sites and of the 1 and 2 tetrahedral sites.

[0016] In the present invention, Algerian bentonites from Maghnia orMostaganem are used as catalysts for the polymerization of certainmonomers, namely cyclic ethers, lactones, olefins, and monomers withvinyl or acrylic groups. Prior to use as a catalyst, bentonites must beactivated with an organic or mineral acid in a selected concentration.This concentration can be determined by one who is skilled in the artwithout undue experimentation. An example demonstrating this process ofactivation is disclosed in Example 1.

Example 1

[0017] Bentonite from Maghnia (20 g) was crushed for 15 minutes using aProlabo ceramic balls grinder. It was then dried by baking at 105° C.for 2 hours. The bentonite was then weighed and placed in an Erlenmeyerflask together with 500 ml of distilled water. The bentonite/watermixture was stirred using a magnetic stirrer and combined with 40 ml ofsulfuric acid. Stirring was stopped and the sulfuric acid/bentonitesolution was allowed to sit for 3 days, following which it was filteredthrough the use of filter paper. The resulting solid was washed withdistilled water, weighed again, and then dried at 150° C. The resultingactivated bentonite catalyst was then stored in a hermetically sealedcontainer.

[0018] The above process for activating a bentonite catalyst may bealtered by stirring the sulfuric acid/bentonite solution, reducing thetreatment time from 3 days to 12 hours. We have also found that byrefluxing the sulfuric acid/bentonite solution while stirring, thetreatment time could be reduced to as little as 2 hours. Theconcentration of the sulfuric acid should preferably be between 0.1 and0.9M. Concentrations above 1M may deactivate the catalytic properties ofthe bentonite. The optimal concentration of sulfuric acid for thepolymerization of THF and 1,3 dioxolane (examples below) is 0.23M, whereconversion rates were optimized.

[0019] Other mineral and organic acids may be used to activate thebentonite catalyst. Examples of these include nitric acid, chloric acid,flouric acid, propionic acid, butyric acid, and acrylic acid. Otheracids and the appropriate concentrations can be determined by those ofordinary skill in the art.

[0020] The monomer can be used as is or can be pretreated by a bentonitefrom Maghnia or Mostaganem. This pretreatment allows for elimination ofthe impurities in the monomer, such as water. An example of thistreatment is contained in Example 2.

Example 2

[0021] Commercial grade THF was analyzed by vapor phase chromatographyand found to contain 7% of impurities and water. Activated bentonite wasthen added to the commercial grade THF in a 0.5:100 activated bentoniteto commercial grade THF ratio. The resulting solution was then boiledfor two hours. The THF was filtered from the resulting solution, driedon magnesium sulfate (MgSO₄) to remove any trace of water and thentested for impurities using gas phase chromatograph. Fewer impuritieswere found.

[0022] The pretreatment step may also be performed within a nitrogen orargon atmosphere for a further reduction in water in the monomer. Thispretreatment step may also be used on other monomers and solvents priorto use in the polymerization reaction with bentonites.

[0023] The activated bentonite catalyst may be used to polymerize avariety of monomers. Examples of several monomers that may bepolymerized are illustrated in the following examples. Variations inreaction conditions and additives will result in differences from theexamples below. For instance, the use of solvents slows down thereaction rate. The temperature influences the polymer molecular weightand its degree of polymerization and polymolecularity (poly-dispersionrate). Higher temperatures will result in a lower molecular weight. Forinstance, for PTHF, the increase in temperature from 30° to 40° C. willresult in a decrease in molecular weight from 4900 to 2400. Highertemperatures will increase the reaction rate. The reactions willgenerally function between the temperatures of −100° C. and 100° C.Stirring has an important effect. With no stirring, the reaction yieldspolymers that have higher molecular weights and higher poly-dispersionrates. With stirring, polymers are produced with lower molecular weightsbut with a polydispersity rate of between 1 and 3.

[0024] Prompt separation of the reaction products from the activatedbentonite catalyst is preferred. Continued contact between the actualbentonite catalyst and the polymer will result in depolymerization.

[0025] Concentrations are indicated in weight and in percent withrespect to weight. Examples 1 through 6 are homopolymers of cyclicethers.

Example 3 Polymerization of THF

[0026] A condenser filled with argon and a magnetic stirrer was mountedon a 250 ml three-neck flask. The following reagents were thenintroduced in the flask: 84.13 g (1.66 mmole) of commercial grade THF,14.02 g (0.137 mmol) of acetic anhydride and 1.99 g of activatedbentonite. The reaction was performed while stirring using the magneticstirrer and at room temperature. The reaction was stopped after 6 hours.The catalyst was then removed through filtration. Remaining THF monomerand acetic anhydride were then evaporated. The polymer was precipitatedin cold methanol, dried and weighed (78.5 g). The compound was yellow tobrown. The poly-THF (PTHF) was analyzed using ¹H NMR (Bruker 200 MHZ)using CHCl₃ as solvent and TMS as reference. The chemical shifts of thevarious groups were found to be: (CH ₂)2—CH₂—: 1.5 (ppm) and —CH₂CH₂O—:3.2 (ppm). The molecular weight values were determined using vaporphase chromatography, calibrated with polystyrene in THF, and found tobe: M_(pic)=7976.4, M_(w)=8748.9; M_(n)=6506.2. The polydispersity index(M_(w)/M_(n)) was calculated as 1.3.

Example 3A

[0027] The experiment in Example 3 was repeated using THF pretreated inaccordance with the procedure demonstrated in Example 2. The PTHFproduced by the reaction was white instead of yellow to brown. The NMRmeasurement gave the same chemical shift as shown in Example 3. Themolecular weight values were again determined by vapor phasechromatography and found to be: M_(pic)=8377.4; M_(w)=9430.1;M_(n)=6537.4. The polydispersity index (M_(w)/M_(n)) was calculated as1.4.

Example 3B

[0028] The experiment in Example 3A was repeated but the aceticanhydride was omitted. No polymerization reaction was observed.

Example 3C

[0029] The experiment in Example 3 was repeated, except thatdichloromethane was added as a solvent. The PTHF was analyzed using NMRand its molecular weight was determined with vapor phase chromatographyand found to be: Molecular weight=7144.4; M_(w)=8436; M_(n)=6501.1. Thepolydispersity index (M_(w)/M_(n)) was calculated as 1.29.

Example 3D

[0030] The experiment in Example 3 was repeated except that the magneticstirrer was omitted. The polymer was analyzed using NMR and itsmolecular weight values were determined using vapor phasechromatography. The values were: Molecular weight=6810.0; M_(w)=8772.3;M_(n)=6471.4 and the polydispersity index (M_(w)/M_(n)) was calculatedas 1.29.

[0031] It is apparent from these experiments that stirring, the use of asolvent, temperature and reaction duration influence the molecularweight and the degree of polymerization (polymolecularity ratio). Thereaction temperature and the amount of the activated bentonite catalystdetermine the length of the PTHF chains, from M_(n)=200 to M_(n)=10000.Further, high temperature during the reaction results in a risk ofreticulation or depolymerization of the acrylic or methacrylicmacromonomers.

[0032] The polymers that result from Examples 3- 3D are telechelics.They have a double bond at the end of each chain. This bond positionallows use of the PTHF as a non-toxic softening agent in the synthesisof various polymers, which are biocompatible and/or biodegradable.Further, the reaction in Examples 3- 3D occurs in a single step incontrast to current methods, which require many steps includingpolymerization of the THF and fixation of polymer groups at the end ofthe chains. The bentonite catalyst does not require an organic solventand is non-toxic.

Example 4 Polymerization of 1,3-dioxolane

[0033] A magnetic stirrer was placed in a 250 ml Erlenmeyer flask withan air atmosphere. While continuously stirring with the magneticstirrer, 500 mg of activated bentonite catalyst and 50 g of1,3-dioxolane were combined in the 250 ml Erlenmeyer flask. The reactionbegan three minutes after combining the two reagents and was violent.The stirring was stopped and the reagents allowed to sit for 10 hours.The reaction products were dissolved in dichloromethane and thebentonite catalyst removed by filtering the solution through filterpaper. The solution was then baked under vacuum at 25° C. After 4 hours,the polydioxolane (PDXL) polymer was weighed (48.8 g) and analyzed usingNMR and vapor phase chromatography, calibrated with polyoxyethylene. TheMolecular weight=8053.5, M_(w)=12469.9, M_(n)=3111.5 and thepolydispersity index (M_(w)/M_(n)) was calculated as 3.97.

Example 4A

[0034] The experiment in Example 4 was repeated with dichloromethane asa solvent. The reaction was stopped after 2 hours, and the solvent wasevaporated under vacuum. The PDXL was then dried as in example 4 andanalyzed by NMR and vapor phase chromatography. The Molecularweight=7976.4, Mw=8748.9, Mn=6506.2 and the polydispersity index(M_(w)/M_(n)) was calculated as 1.3.

[0035] The reactions described in Examples 4 and 4A are temperaturesensitive. Reactions at temperatures below 0° C. yield a high M_(n)(M_(n)>56,000). The M_(n) drops as the temperature increases above 0° C.The amount of catalyst also drives the resulting M_(n). M_(n) increaseslinearly with the catalyst concentration up to a critical value, 5% ofcatalyst concentration. Beyond such a value M_(n) does not vary anddepolymerization may result. If a solvent such as dichloromethane isadded to the solution there is a noticeable depolymerization rate.

Example 5 Polymerization of epichlorohydrin

[0036] A magnetic stirrer was placed in a 250 ml Erlenmeyer flask withan air atmosphere. While continuously stirring with the magneticstirrer, 100 mg of activated bentonite catalyst and 10 g ofepichlorohydrin were combined in the 250 ml Erlenmeyer flask. Thereaction was immediate and violent and resulted in a black product. Theproduct was dissolved in chloroform, and passed through an activatedcarbon bed. The bentonite catalyst was filtered, resulting in a yellowsolution. The solvent was then evaporated and a highly viscous polymerremained. The poly-epichlorohydrin was then weighed (9.3 g). Thepoly-epichlorohydrin was then analyzed by NMR resulting in a single peakat 3.76 PPM and the molecular weight of the polymer was determined to be654 by viscometry (capillary viscometer SEMATECH) at 25° C. inchloroform. M_(v) was 654; M_(n)=726; M_(w)=2046. After precipitation inmethane, M_(n)=3450; M_(w)=5390.

Example 5A

[0037] The experiment in Example 5 was repeated using epichlorohydrinpretreated in accordance with the procedure demonstrated in Example 2.The chemical shifts were identical to those obtained in Example 5. Themolecular weight was determined by viscometry to be 865.

Example 6 Polymerization of 1,2-epoxypropane

[0038] A magnetic stirrer was placed in a glass-stoppered 100 mlErlenmeyer flask with an air atmosphere. While continuously stirringwith the magnetic stirrer, 100 mg of activated bentonite catalyst and 5g of 1,2-epoxypropane were combined in the 100 ml Erlenmeyer flask. Assoon as the two reagents were added, a violent reaction resulted, heatwas released, and the solution turned black. Chloroform and vegetalcarbon were added to remove impurities resulting from reaction. Afterstirring the solution was passed through filter paper to remove thebentonite catalyst. The chloroform was then evaporated in low vacuum toextract the poly-1,2-epoxypropane. The resulting polymer was weighed(3.9 g) and then analyzed using NMR. NMR results were a CH₃ (doublet) at5.1 ppm and —CH₂ and —CH—O—(multiplet) at 3.2-3.8 ppm. M_(v) was 520(viscometric value). Viscometry measured a molecular weight of 420 forthe poly-1,2-epoxypropane.

Experiment 6A

[0039] The experiment in Example 6 was repeated using 1,2-epoxypropanepretreated in accordance with the procedure demonstrated in Example 2.The poly-1,2-epoxypropane was analyzed using NMR and its molecularweight was determined by viscometry to be 640.

[0040] One of ordinary skill in the art will recognize that othermonomers such as ethylene oxide, oxetane, 1,3 dioxepane, 1,3 dioxocane,and their substitutents; lactams including 3-propanolactam;4-butanolactam; 5-pentanolactame and 6-hexanolactam; lactones includingcaprolactone, and valerolactone; aldehydes including acetaldehyde,propionaldehyde and butyraldehyde; and non-cyclic ethers includingchloroethyl vinyl ether, butyl vinyl ether and ethyl vinyl ether may beused in a manner similar to that shown above.

[0041] Example 7 is an experiment showing the use of the Maghnia orMostaganem bentonite to form a copolymer of two cyclic ethers.

Example 7 Copolymerization of 1,3-ioxolane and 1,3,5 trioxane

[0042] A magnetic stirrer was placed in a 100 ml Erlenmeyer flask withan air atmosphere. While continuously stirring with the magneticstirrer, 5 g of 1,3-dioxolane and 5 g of 1,3,5 trioxane were mixed in a100 ml Erlenmeyer flask. 100 mg of activated bentonite catalyst was thenadded to the mixture. The reaction was then allowed to proceed for 2hours while constantly stirring. The bentonite catalyst was extractedfrom the reaction solution by filtration with filter paper andchloroform, which was evaporated under vacuum. The copolymer of1,3-dioxolane and 1,3,5 trioxane was weighed (7.2 g) and then analyzed.All the chemical shifts agree with those reported in the literature. Themolecular weight was determined by viscometry in THF at 25° C. to be830.

[0043] One of ordinary skill in the art will recognize that othermonomers such as butadiene, divinyl benzene and other monomers with twoconjugated double bonds may be used in a manner similar to that shownabove.

[0044] In a manner similar to that shown above for the polymerization ofcyclic ethers, the activated bentonite catalyst can be used to reacttoxic substances such as dioxin and its derivatives to form non-toxiccompounds. A series of examples of this process are shown in Example 8.

Example 8

[0045] Gaseous NH₃ was incorporated into the bentonite catalyst. Dioxanewas added to the gaseous NH/bentonite catalyst mixture for two hours.The resulting product was extracted from the bentonite catalyst andfound to have one or more of the oxygen atoms on the carbon/oxygen ringsubstituted by nitrogen atoms to form morpholine (where one oxygen atomwas substituted) and piperazine (where both oxygen atoms weresubstituted).

Example 8A

[0046] A chlorinated aromatic molecule was added to a treated bentonitecatalyst, which had been previously reacted with an amine. The resultingreaction was carried out at 30° C. The reaction product was thenextracted with cholorform.

[0047] Derivatives of dioxin, DDT and PCB's may be reacted in much thesame way as examples 8 and 8A to form non-toxic reaction products.

[0048] Example 9 is an experiment showing the use of the Maghnia orMostaganem bentonite to polymerize styrene, a monomer having a vinylgroup.

Example 9 Polymerization of styrene

[0049] A magnetic stirrer was placed in a glass-stoppered 10 mlErlenmeyer flask with an air atmosphere. While continuously stirringwith the magnetic stirrer, 100 mg of activated bentonite catalyst and 10g of styrene were combined in the 100 ml Erlenmeyer flask. The reactionwas exothermic and resulted in a solution that became solid with aslightly yellowish color. The polystyrene was then dissolved inchloroform and the bentonite catalyst recovered by filtration. Thechloroform was evaporated under vacuum, leaving the polystyrene. Thepolymer was characterized by NMR ¹H, GPC and DSC. The conversion rate isapproximately 80%. The derivative monomers of styrene have essentiallythe same behavior.

[0050] One of ordinary skill in the art will recognize that othermonomers with vinyl groups such as styrene derivatives, vinyl ethers anddivinylbenzene may be used in a manner similar to that shown above.M_(n) increases for low temperatures (close to 0° C.) and decreases forhigher temperatures (>50° C.). An increase in the activated bentonitecatalyst concentration favors the creation of higher M_(n) up to acritical concentration of 5% of catalyst with respect to molecularweight. Above that value the M_(n) is stable.

[0051] The polystyrene polymers obtained have a glass temperature(vitrification) (T_(g)) that increase with M_(n). The T_(g)'s vary from80° C. to 125° C. The polystyrene produced by the bentonite catalystshave a syndiotactic structure. The method described above forpolymerizing polystyrene is an improvement over the current methods interms of both cost and ease of operation. Current methods use CH₂Cl₂ at−80° C. and require BF₃ or triflic acid for polymerization of styrene.

Example 10 Polymerization of Isobutylene

[0052] The un-activated bentonite catalyst was dried under vacuum.Isobutylene was then condensed at low temperatures in the reactor. Thereaction was initiated using mechanical agitation. After approximately 4hours, an oily mixture was collected. NMR analysis of this mixturerevealed that the oily mixture contained a telechelic oligomer ofisobutylene.

Example 10A

[0053] The experiment in example 10 was repeated, but by first adding asolvent to the isobutylene and then agitating the mixture. Theconversion rate is higher than in Example 10, 83% with a solvent, 10%without a solvent at 10° C., with a reaction duration of 3 hours and 30minutes.

[0054] The results of Examples 10 and 10A may be altered by changingeither the temperature or catalyst content. The high temperature limitis fixed by the stability of isobutylene. Temperatures above the boilingpoint of about −26° C. may not be used. Low temperatures yield viscousoils with much higher masses. When the amount of the activated bentonitecatalyst is decreased, M_(n) increases as well. Molecular weights alsoincrease with the use of solvents.

[0055] One of ordinary skill in the art will recognize that otherolefinic monomers such as ethylene, proplylene, normal butene and dienessuch as butadiene, isoprene, and chloroprene may be used in a mannersimilar to that shown above.

Example 11 Synthesis of Perflourinated Amines and Diamines

[0056] Morpholine, a secondary amine, was added to an activatedbentonite catalyst and agitated. An iodoperfluoroalkyl(CF₃—(CF₂)_(n)—CF₂I) was then stirred into the mixture and was absorbedby the activated bentonite catalyst. The reaction was allowed tocontinue for 8 hours. The perfluouoamine iodide salt was then extractedfrom the activated bentonite catalyst with cholorform. The resultingproduct was found to have the following structure:(CF₃—(CF₂)_(n)—CF₂I)—N⁺H—(CH₂CH₂)₂X, I⁺ where X was either oxygen or NH.This product was then neutralized in a basic solution to obtain theperflourinated amine.

Example 11A

[0057] The experiment in example 11 was repeated, but diodoperfluoralkyl (ICF₂—(CF₂)_(n)—CF₂I) and piperazine were used in place ofthe iodoperfluoroalkyl (CF₃—(CF₂)_(n)—CF₂I). After extraction withchloroform, a perflourinated piperazine was identified with thestructure:

[0058] ˜CF₂—N⁺—(CH₂CH₂)N⁺H—CF₂(CF₂)_(n)CF₂

[0059] I⁻ I⁻

[0060] Example 12 is an experiment showing the use of Maghnia orMostaganem bentonite to polymerize lactides into polylactides, oftentermed “bio-compatible polymers” for such uses as stitching for surgery.

Example 12

[0061] The bentonite was dried under vacuum at 105° C. and then wascooled under vacuum. A cyclic lactide was then added to the driedbentonite catalyst. The dried bentonite/cyclic lactide mixture was thenheated under vacuum until the mixture melted. The melting temperaturewas then maintained for approximately four hours, and then cooled toroom temperature under vacuum. The dried bentonite catalyst/polycycliclactide was then dissolved in a solvent. The dried bentonite catalystwas then removed by filtration and the polycyclic lactide wasprecipitated in a non-solvent.

[0062] Any appropriate solvent may be used to issolved the driedbentonite catalyst/polycyclic lactide. Examples include both ethyl etherand dichloromethane. Further, if desired, the need for both the solventand the precipitating non-solvent may be forgone with separation usingheating and filtration under vacuum.

[0063] Other modifications of the invention described above will beobvious to those skilled in the art, and it is intended that the scopeof the claims be limited only as set forth in the appended claims.

What is claimed is:
 1. A bentonite catalyst manufactured by the processcomprising: contacting a Maghnia or Mostaganem bentonite with an acidsolution of selected concentration; and drying the Maghnia or Mostaganembentonite.
 2. A catalyst manufactured by the process in claim 1 whereinthe acid is sulfuric acid and the selected concentration is 0.2-0.9 M..3. A catalyst manufactured by the process in claim 1 wherein the Maghniaor Mostaganem bentonite is dried between 105° C. and 150° C.
 4. Aprocess for polymerizing vinyl, acrylic, cyclic ether, non-cyclic vinylether, aldehyde, lactone or olefin monomers comprising: contacting aMaghnia or Mostaganem bentonite with an acid solution of selectedconcentration; drying the Maghnia or Mostaganem bentonite; andcontacting the vinyl, acrylic, cyclic ether, aldehyde, lactone, orolefin monomer with the Maghnia or Mostaganem bentonite.
 5. A process inaccordance with claim 4 wherein the Maghnia or Mostaganem bentonite hasa SiO₂ concentration of greater than 65% by weight.
 6. A process inaccordance with claim 4 wherein prior to contacting a Maghnia orMostaganem bentonite with an acid solution of selected concentration:contacting the vinyl, acrylic, cyclic ether, non-cyclic vinyl ether,aldehyde, lactone or olefin monomer with a Maghnia or Mostaganembentonite; boiling the vinyl, cyclic ether, non-cyclic vinyl ether,aldehyde, lactone, acrylic or olefin monomer; and filtering the vinyl,cyclic ether, non-cyclic vinyl ether, aldehyde, lactone, acrylic orolefin monomer to remove the Maghnia or Mostaganem bentonite.
 7. Aprocess in accordance with claim 4 wherein after drying the Maghnia orMostaganem bentonite and before contacting the vinyl, acrylic, cyclicether, non-cyclic vinyl ether, aldehyde, lactone or olefin monomer witha Maghnia or Mostaganem bentonite, placing the Maghnia or Mostaganembentonite within an argon or nitrogen atmosphere.
 8. A process inaccordance with claim 4 wherein the cyclic ether monomer istetrahydrofuran.
 9. A process in accordance with claim 4 wherein thecyclic ether monomer is 1,3 dioxolane.
 10. A process in accordance withclaim 4 wherein the cyclic ether monomer is epichlorohydrin.
 11. Aprocess in accordance with claim 4 wherein the cyclic ether monomer is1,2 epoxypropane.
 12. A process in accordance with claim 4 wherein thecyclic ether monomers are 1,3 dioxolane and 1,3,5 trioxane.
 13. Aprocess in accordance with claim 4 wherein the vinyl monomer is styrene.14. A process in accordance with claim 4 wherein the olefin monomer isan alpha olefin.
 15. A process in accordance with claim 14 wherein thealpha olefin is isobutylene.
 16. A process in accordance with claim 4wherein the olefin monomer is a diene.
 17. A process for synthesizing aperflourinated amine or diamine comprising: contacting a Maghnia orMostaganem bentonite with an acid solution of selected concentration;drying the Maghnia or Mostaganem bentonite; adsorbing a secondary amineon the Maghnia or Mostaganem bentonite to form a perflouroamide iodidesalt; extracting the perflouramide idodide salt with a polar solvent;and neutralizing the perflouramide iodide salt with a basic solution toform the perflouramide or diamine.
 18. A process in accordance withclaim 17 wherein the polar solvent is chloroform.
 19. A process inaccordance with claim 17 wherein the secondary amine is morpholine,pyrolidinone, piperazine, or piperidone.
 20. A process in accordancewith claim 17 wherein the secondary amines are diodo-perfluoroalkyl andpiperazine.
 21. A polymer manufactured by the process comprising:contacting a Maghnia or Mostaganem bentonite with an acid solution ofselected concentration; drying the Maghnia or Mostaganem bentonite; andcontacting a vinyl, cyclic ether, non-cyclic vinyl ether, aldehyde,lactone, acrylic or olefin monomer with the Maghnia or Mostaganembentonite.
 22. A polycyclic lactide manufactured by the processcomprising: drying a Maghnia or Mostaganem bentonite; contacting alactide with the Maghnia or Mostaganem bentonite to form a polycycliclactide/ Maghnia or Mostaganem bentonite mixture; and separating thepolycyclic lactide from the polycyclic lactide/Maghnia or Mostaganembentonite mixture.